Valorization of Purple Phototrophic Bacteria Biomass Resulting from Photo Fermentation Aimed at Biohydrogen Production.

This study evaluated the feasibility of contextually producing hydrogen, microbial proteins, and polyhydroxybutyrate (PHB) using a mixed culture of purple phototrophic bacteria biomass under photo fermentative conditions. To this end, three consecutive batch tests were conducted to analyze the biomass growth curve and to explore the potential for optimizing the production process. Experimental findings indicated that inoculating reactors with microorganisms from the exponential growth phase reduced the duration of the process. Furthermore, the most effective approach for simultaneous hydrogen production and the valorization of microbial biomass was found when conducting the process during the exponential growth phase of the biomass. At this stage, achieved after 3 days of fermentation, the productivities of hydrogen, PHB, and microbial proteins were measured at 63.63 L/m3 d, 0.049 kg/m3 d, and 0.045 kg/m3 d, respectively. The biomass composition comprised a total intracellular compound percentage of 56%, with 27% representing PHB and 29% representing proteins. Under these conditions, the estimated daily revenue was maximized, amounting to 0.6 $/m3 d.

Role of organic nanoparticles on transport and fate of various dyes in aqueous solution.

This work studies the interaction of organic nanoparticles (ON) with various dyes in aqueous solution, to elucidate the role of ON on transport and fate of dyes in the environment, and on dyes removal from wastewater. Studied dyes are Acid Red 66 (AR66), Methylene Blue (MB), Reactive Black 5 (RB5), and Reactive Violet 5 (RV5). ON are extracted from organic matter of anthropogenic origin through resuspension of its colloidal fraction, and successive filtration and dialysis of the obtained suspension. Mechanisms of interaction are investigated initially through three-dimensional excitation emission matrix (3DEEM) analysis. Obtained data indicate that dynamic interactions occur strongly between dye molecules and ON aggregates. 3DEEM spectra of mixed samples containing ON together with one of the tested dyes, present a shape similar to the one of ON alone, but each of them is characterized by specific differences in terms of peaks quenching and shift. The analysis of these singularities suggests that dye molecules are bound to the functional groups of ON through H-bonds, according to the following steps: i) dyes reach the surface of ON aggregates; ii) the molecules pass through the hydrophilic surface of ON aggregates, and reach their hydrophobic core; iii) the dyes are sequestrated into the hydrophobic core of ON aggregates. Nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopies analysis confirm the formation of supramolecular aggregates with stable micellar hydrophobic structure, mainly consisting of aliphatic fractions of ON, which explain the disappearance of aromatic groups signals from dyes.

A comprehensive review of mathematical models of photo fermentation.

This work aims at analyzing and comparing the different modeling approaches used to date to simulate, design and control photo fermentation processes for hydrogen production and/or wastewater treatment. The study is directed to researchers who approach the problem of photo fermentation mathematical modeling. It is a useful tool to address future research in this specific field in order to overcome the difficulty of modeling a complex, not totally elucidate process. We report a preliminary identification of the environmental and biological parameters, included in the models, which affect photo fermentation. Based on model features, we distinguish three different approaches, i.e. kinetic, parametric and non-ideal reactors. We explore the characteristics of each approach, reporting and comparing the obtained results and underlining the differences between models, together with the advantages and the limitations of each of them. The analysis of the approaches indicates that Kinetic models are useful to describe the process from a biochemical point of view, without considering bio-reactor hydrodynamics and the spatial variations that Parametric Models can be utilized to study the influence and the interactions between the operational conditions. They do not take into account the biochemical process mechanism and the influence of reactor hydrodynamics. Quite the opposite, non-ideal reactors models focus on the reactor configuration. Otherwise, the biochemical description of purple non-sulfur bacteria activities is usually simplified. This review indicates that there still is a lack of models that fully describe photo fermentation processes.

Supramolecular aggregation of colloidal natural organic matter masks priority pollutants released in water from peat soil.

Natural organic matter (NOM) from Sphagnum peat soil is extracted in water and subjected to several investigations to obtain structural and conformational information. Data show that the extracted NOM is self-organized in colloidal aggregates of variable sizes (from nano to micro scales, depending on the solvent composition, i.e., ultrapure water, solutions with denaturing agents, acetone, ethanol). Aggregates are formed by highly heterogeneous classes of organic compounds. According to the results of nuclear magnetic resonance and fluorescence measurements, the three-dimensional structure of aggregates, revealed by scanning electron microscope imaging, is supposed to be stabilized by the exposition of polar functional groups to the solvent, with consequent formation of hydrogen bonds, dipole-interactions and cation bridging. In contrast, the inner part of the aggregates displays hydrophobic features and is hypothesized to be further reinforced by the establishment of π-stacking interactions. The structure is assumed to be a supramolecular aggregation of small-medium oligomeric fragments (Max 750 Da) in which priority pollutants are entrapped by dispersive forces. The structures are shown to be nanosized spheroidal particles further aggregated to form higher dimension supra-structures. Carbohydrates play primary role, stabilizing the structure and giving marked hydrophilic properties to the aggregates.

Carbon catabolite repression occurrence in photo fermentation of ethanol-rich substrates.

The paper investigates the phenomenon of Carbon Catabolite Repression occurring during photo fermentation of ethanol-rich effluents, which usually contain ethanol as main carbon source, and glycerol as secondary one. The study was conducted using mixed phototrophic cultures, adopting, as substrate, the effluent produced by the alcoholic fermentation of sugar cane bagasse. In order to elucidate the phenomenon, experimental tests were carried out using two different ethanol to glycerol ratios. Results were compared with those resulting from pure ethanol and glycerol conversion. According to the obtained data, as a result of Carbon Catabolite Repression occurrence, the presence of glycerol negatively affects hydrogen production. Indeed, part of the ethanol source is converted to biomass and polyhydroxybutyrate rather than to hydrogen. In more details, the presence of glycerol determines a drop of the hydrogen production, which goes from 12 % to 32 %, according to the ethanol/glycerol ratio, compared to the production obtained from fermentation of ethanol alone. Therefore, to promote the hydrogen production, it is advisable to apply strategies to produce low glycerol concentrations in the ethanol production stage.

Biohydrogen and poly-ß-hydroxybutyrate production by winery wastewater photofermentation: Effect of substrate concentration and nitrogen source.

The applicability and convenience of biohydrogen and poly-ß-hydroxybutyrate production through single-stage photofermentation of winery wastewater is demonstrated in the present study. Experiments are conducted using a purple non-sulfur bacteria mixed consortium, subject to variable nutrient conditions, to analyze the effect of initial chemical oxygen demand and the available nitrogen source on the metabolic response. Results show that winery wastewater is a promising substrate for photofermentation processes, despite the presence of inhibiting compounds such as phenolics. Nonetheless, the initial chemical oxygen demand must be carefully controlled to maximize hydrogen production. Up to 468 mL L-1 of hydrogen and 203 mg L-1 of poly-ß-hydroxybutyrate can be produced starting from an initial chemical oxygen demand of 1500 mg L-1. The used nitrogen source may direct substrate transformation through different metabolic pathways. Interestingly, the maximum production of both hydrogen and poly-ß-hydroxybutyrate occurred when glutamate was used as the nitrogen source.

Evaluation of the potential for caesium transfer from contaminated soil to the food chain as a consequence of uptake by edible vegetables.

This paper analyzes the effect of caesium (Cs) concentration on seed germination, seedling growth, root uptake, and leaf uptake of Lactuca sativa to understand the potential transfer of the metal from contaminated soil to humans through the food chain. The results of germination experiments show that seed germination and seedling growth strongly depend on increasing Cs concentration, with a decrease in the number of germinated seeds compared to the control up to 13.6% and a reduction in seedling growth up to 10.3% at the highest Cs tested concentration (15 mM). Uptake experiments indicate a low transfer of Cs from soil to leaves and roots of the plants, ranging between 0.06% and 2.2%. The transfer is found to be a not-monotone function of soil potassium (K) content, with highest values corresponding to 1-2 mM K2SO4. Increasing concentrations of K lead to lower translocation of Cs from roots to leaves. Values above the average amount applied (20 and 40 mM K2SO4) almost stop the translocation, suggesting the use of a high amount of K2SO4 protects the food chain from Cs contamination.

Assessment of metal pollution in the Lambro Creek (Italy).

This study assessed the effect of metal pollution in the Lambro Creek (Southern Italy). Water, sediment and biota were collected at six sampling sites (June) for metal concentration assessment (Cr, Cu, Ni, Pb and Zn). Sequential extraction was performed to determine the distribution of metals in different geochemical sediment fractions. The influence of pH and leaching time on the release of metals from sediment to the water column was investigated via remobilization tests. A battery of toxicity tests (Vibrio fischeri, Raphidocelis subcapitata, Phaeodactylum tricornutum, and Daphnia magna) with multi-endpoints (bioluminescence, growth inhibition, and immobilization) was used to determine the overall toxicity in sediment water extracts. The results showed that metals did not exceed the probable effect concentration levels, with Cr concentration exceeding the threshold effect concentration level at all sampling points except for the one closer to the source of the creek, suggesting potential negative effect on the biota. Considering the cumulative criterion unit, sediment contamination was moderate at all sampling sites, except for L3 and L5 where biota was exposed to a very high risk. With respect to sequential analysis, the most readily available fraction of metal can be generalised as Ni > Cr > Cu > Zn > Pb. For better understanding the fate of metals in the water-sediment environment, their biogeochemical cycles should also be investigated in small creeks including both fresh (watercourse) and saltwater (river mouth) sediments.

Optimization of Soil Washing to Reduce the Selenium Levels of Seleniferous Soil from Punjab, Northwestern India.

Seleniferous soil collected from the wheat ( L.)-grown agricultural land in Punjab, India, was characterized and the Se concentration in various soil fractions was determined by sequential extraction. The soil had a total Se content of 4.75 (±0.02) mg kg, of which 44% was observed in the oxidizable soil fraction. Soil flushing as an in situ technique was performed to simulate the Se migration pattern in case of rainfall or irrigation. Significant migration of Se from the upper layer to the lower layers was observed during water percolation through the soil column at a flow rate of 1 mL min, which could be attributed to Se reduction in the lower anoxic layers of the soil column. For ex situ treatment, the soil washing technique was optimized by varying different parameters such as treatment time, temperature, pH, liquid to solid (L:S) ratio, and presence of competing ions and oxidizing agents. Selenium extraction from soil was significantly improved by the presence of oxidizing agents in the washing solution: ∼38% Se was removed from the soil in the presence of 0.5% KMnO. In contrast, parameters such as treatment time, temperature, pH, L:S ratio, and competing ions did not significantly enhance the Se extraction efficiency. In this research, laboratory-scale in situ and ex situ treatment techniques for Se removal from soil were studied and optimized. The results provide an insight for large-scale Se removal and recovery from seleniferous soils.

Sequential application of soil washing and phytoremediation in the land of fires.

This paper presents an experimental study aimed at verifying the efficiency of a double-stage remediation process to be applied in former agricultural sites contaminated by illegal dumping of industrial wastes. The process, which includes an EDDS (Ethylenediamine-N,N'-disuccinic acid) enhanced washing, followed by a phytoremediation treatment, is applied at the lab scale for the remediation of a soil sampled in a territory known as Land of Fires (Italy) contaminated with Cu (∼400 mg kg-1) and Zn (∼250 mg kg-1). Phytoremediation is conducted using Lactuca sativa to verify, together with process efficiency, the potential risks due to metal accumulation in edible species. The results of the washing process show the possibility of removing the potential toxic metals from 44% to 77% for Cu and from 18% to 47% for Zn. The removal is well distributed among all soil fractions. There is almost no removal of other components which are fundamental for an agricultural soil. Results of the subsequent phytoremediation treatment indicate that both the contaminants and the residual EDDS/EDDS-chelates adsorbed into the soil generally negatively affect plant growth, reducing the number of germinated seeds up to 43%, and the shoot length up to 63%. Nonetheless, whenever the efficiency of the washing stage is high enough, no adverse effect is obtained on the plants. The efficiency of the phytoremediation stage mainly relies on leaf uptake, which accounts for up to 88% of the total removed Cu and up to 95% of the total removed Zn. Stabilization in the underground part of the plant is more contained because of the limited mass of the roots.

Application of an electrochemical treatment for EDDS soil washing solution regeneration and reuse in a multi-step soil washing process: Case of a Cu contaminated soil.

Soil washing is an extensively used process for remediation of heavy metals contaminated soils. However the amount of fresh washing solution to be used represents a significant economical drawback of this process. This paper investigates the application of an electrochemical process (Fe/Fe electrodes couple) for the regeneration of a spent EDDS solution, containing Cu and major competitor cations (Ca, Fe, Mg, and Mn). The effect of current density, pH and conductivity of the washing solution on the recovery process performances was investigated. Current density showed the highest influence on Cu, Mg and Mn removal yields. Maximum removal yields reached 99% for Cu, 77% for Mn and 49% for Mg. No influence of the investigated parameters on Ca removal was observed, while an increase of Fe concentration due to anode dissolution occurred. Characterization of sludge produced from the 2 h electrochemical test (5 mA cm(-2), pH = 8, 8 mS cm(-1)) displayed concentrations of 2.8 g kg(-1) for Ca, 0.4 g kg(-1) for Cu, 535.6 g kg(-1) for Fe, 2.6 g kg(-1) for Mg. TCLP tests at pH 2.88 and 4.93 showed a low leaching percentage (Ca, 10-21%; Cu, 6-12%; Fe, 0.22% Mg, 27-36%). Multi-washing tests were carried out to assess the decrease of the chelating ability of the regenerated washing solution and the Cu extraction efficiency.

Optimization of the treatment cycle of pressed-off leachate produced in a facility processing the organic fraction of municipal solid waste.

The paper investigates, at a laboratory scale, the applicability of anaerobic digestion for the treatment of pressed-off leachate produced in a biomechanical treatment plant for municipal solid waste. Batch tests show that the anaerobic process proceeds smoothly and produces about 10,000 mL of methane per litre of treated leachate. The process is characterized by a lag phase lasting about 30 days, and is completed in about 2 months. Chemical oxygen demand (COD) and volatile fatty acids monitoring allows studying process kinetics that are modelled through a triple linear expression. Physical and biological treatments are also investigated to reduce the residual organic charge of the produced digestate. The best performances are obtained via aerobic degradation followed by assisted sedimentation. This cycle reduces the residual COD of about 85%, and allows the correct disposal of the final waste stream.

Thermal pretreatment of olive mill wastewater for efficient methane production: control of aromatic substances degradation by monitoring cyclohexane carboxylic acid.

Anaerobic digestion is investigated as a sustainable depurative strategy of olive oil mill wastewater (OOMW). The effect of thermal pretreatment on the anaerobic biodegradation of aromatic compounds present in (OMWW) was investigated. The anaerobic degradation of phenolic compounds, well known to be the main concern related to this kind of effluents, was monitored in batch anaerobic tests at a laboratory scale on samples pretreated at mild (80±1 °C), intermediate (90±1 °C) and high temperature (120±1 °C). The obtained results showed an increase of 34% in specific methane production (SMP) for OMWW treated at the lowest temperature and a decrease of 18% for treatment at the highest temperature. These results were related to the different decomposition pathways of the lignocellulosic compounds obtained in the tested conditions. The decomposition pathway was determined by measuring the concentrations of volatile organic acids, phenols, and chemical oxygen demand (COD) versus time. Cyclohexane carboxylic acid (CHCA) production was identified in all the tests with a maximum concentration of around 200 µmol L(-1) in accordance with the phenols degradation, suggesting that anaerobic digestion of aromatic compounds follows the benzoyl-CoA pathway. Accurate monitoring of this compound was proposed as the key element to control the process evolution. The total phenols (TP) and total COD removals were, with SMP, the highest (TP 62.7%-COD 63.2%) at 80 °C and lowest (TP 44.9%-COD 32.2%) at 120 °C. In all cases, thermal pretreatment was able to enhance the TP removal ability (up to 42% increase).

Modified Anaerobic Digestion Model No.1 for dry and semi-dry anaerobic digestion of solid organic waste.

The role of total solids (TS) content in anaerobic digestion of selected complex organic matter, e.g. rice straw and food waste, was investigated. A range of TS from wet (4.5%) to dry (23%) was evaluated. A modified version of the Anaerobic Digestion Model No.1 for a complex organic substrate is proposed to take into account the effect of the TS content on anaerobic digestion. A linear function that correlates the kinetic constants of three specific processes (i.e. disintegration, acetate and propionate up-take) was included in the model. Results of biomethanation and volatile fatty acids production tests were used to calibrate the proposed model. Model simulations showed a good agreement between numerical and observed data.

Effect of moisture on disintegration kinetics during anaerobic digestion of complex organic substrates.

The role of the moisture content and particle size (PS) on the disintegration of complex organic matter during the wet anaerobic digestion (AD) process was investigated. A range of total solids (TS) from 5% to 11.3% and PS from 0.25 to 15 mm was evaluated using carrot waste as model complex organic matter. The experimental results showed that the methane production rate decreased with higher TS and PS. A modified version of the AD model no.1 for complex organic substrates was used to model the experimental data. The simulations showed a decrease of the disintegration rate constants with increasing TS and PS. The results of the biomethanation tests were used to calibrate and validate the applied model. In particular, the values of the disintegration constant for various TS and PS were determined. The simulations showed good agreement between the numerical and observed data.

Effect of total solids content on methane and volatile fatty acid production in anaerobic digestion of food waste.

This work investigates the role of the moisture content on anaerobic digestion of food waste, as representative of rapidly biodegradable substrates, analysing the role of volatile fatty acid production on process kinetics. A range of total solids from 4.5% to 19.2% is considered in order to compare methane yields and kinetics of reactors operated under wet to dry conditions. The experimental results show a reduction of the specific final methane yield of 4.3% and 40.8% in semi-dry and dry conditions compared with wet conditions. A decreasing trend of the specific initial methane production rate is observed when increasing the total solids concentration. Because of lack of water, volatile fatty acids accumulation occurs during the first step of the process at semi-dry and dry conditions, which is considered to be responsible for the reduction of process kinetic rates. The total volatile fatty acids concentration and speciation are proposed as indicators of process development at different total solids content.

Selecting for a high lipid accumulating microalgae culture by dual growth limitation in a continuous bioreactor.

A dual-growth-limited continuous operated bioreactor (chemostat) was used to enhance lipid accumulation in an enrichment culture of microalgae. The light intensity and nitrogen concentration where both limiting factors resulting in high lipid accumulation in the mixed culture. Both conditions of light and nitrogen excess and deficiency were tested. Strategies to selectively enrich for a phototrophic lipid-storing community, based on the use of different nitrogen sources (ammonium vs. nitrate) and vitamin B supplementation in the growth medium, were evaluated. The dual limitation of both nitrogen and light enhanced the accumulation of storage compounds. Ammoniacal nitrogen was the preferred nitrogen source. Vitamin B supplementation led to a doubling of the lipid productivity. The availability of vitamins played a key role in selecting an efficient lipid-storing community, primarily consisting of Trebouxiophyceae (with an 82 % relative abundance among eukaryotic microorganisms). The obtained lipid volumetric productivity (387 mg L-1 d-1) was among the highest reported in literature for microalgae bioreactors. Lipid production by the microalgae enrichment surpassed the efficiencies reported for continuous microalgae pure cultures, highlighting the benefits of mixed-culture photo-biotechnologies for fuels and food ingredients in the circular economy.

An environmental friendly cycle for Cr(III) removal and recovery from tannery wastewater.

Results of a lab-scale experimental study are presented that aim to verify the use of ground shrimp shells, not otherwise conditioned, as an adsorbent material to remove chromium(III) from tannery wastewater. The obtained removal efficiency is found to be always over 90%, confirming the capacity of the tested materials to remove chromium(III). The adsorption process is well described by the Brauner-Emmett-Teller isotherm, indicating the existence of both weak and strong adsorption sites inside the shells. Kinetic tests allow to verify that the removal process takes place rapidly during the first 2 h and then tends to reach a plateau: the pseudo second-order model is found to be able to simulate with good approximation, the adsorption process. Analyses comparing the treatment process using shrimp shells vs. other chemical products frequently used for chromium removal, supported by microscopic observations, indicate that the efficiency obtained using shrimp shell is comparable to the efficiency obtained using sodium bicarbonate and sodium hydroxide, but the removal mechanism is different as the adsorption on the polysaccharidic matrix of the shells prevails over the precipitation of chromium salts. The skin tanned with recovered chromium is found to be of low quality; on the contrary satisfying tanning results are obtained using, as tanning agent, the sludge produced by the adsorption process without any further treatment, except for pH correction.

A mechanistic mathematical model for photo fermentative hydrogen and polyhydroxybutyrate production.

An original mathematical model describing the photo fermentation process is proposed. The model represents the first attempt to describe the photo fermentative hydrogen production and polyhydroxybutyrate accumulation, simultaneously. The mathematical model is derived from mass balance principles and consists of a system of ordinary differential equations describing the biomass growth, the nitrogen and the substrate degradation, the hydrogen and other catabolites production, and the polyhydroxybutyrate accumulation in photo fermentation systems. Moreover, the model takes into account important inhibiting phenomena, such as the self-shading and the substrate inhibition, which can occur during the evolution of the process. The calibration was performed using a real experimental data set and it was supported by the results of a sensitivity analysis study. The results showed that the most sensitive parameters for both hydrogen and PHB production were the hydrogen yield on substrate, the catabolites yield on substrate, and the biomass yield. Successively, a different experimental data set was used to validate the model. Performance indicators showed that the model could efficiently be used to simulate the photo fermentative hydrogen and polyhydroxybutyrate production by Rhodopseudomonas palustris. For instance, the index of agreement of 0.95 was observed for the validated hydrogen production trend. Moreover, the model well predicted the maximum PHB accumulation in bacterial cells. Indeed, the predicted and observed accumulated PHB were 4.5 and 4.8%, respectively. Further numerical simulations demonstrated the model consistency in describing process inhibiting phenomena. Numerical simulations showed that the acetate and nitrogen inhibition phenomena take place when concentrations are higher than 12.44 g L-1 and lower than 4.76 mg L-1, respectively. Finally, the potential long term hydrogen production from accumulated polyhydroxybutyrate in bacterial cells was studied via a fast-slow analysis technique.

Assessment of environmental parameters effect on potentially toxic elements mobility in foreshore sediments to support marine-coastal contamination prediction.

Potentially toxic elements (PTEs) presence in marine sediments can significantly affect the environmental quality and negatively influence economy and recreational activities in related areas. Accordingly, contamination monitoring and control in the marine environment is a fundamental task. In this work, four PTEs behavior (i.e. As, Hg, Pb, and Zn) in sandy foreshore sediments (SFSs) was thoroughly investigated at different pH, redox potential and temperature conditions of the marine water. For all the tests, the released As was 2.7-6 times higher than its initial concentration in water. Nonetheless, final mass balances showed that preferential release in the liquid phase occurred for Pb and Hg (up to 10 % and 9.1 %, respectively). Moreover, final Zn and Hg content increase in SFSs labile fractions indicated their higher bioavailability after the tests. The obtained results outline an approach useful to predict the contaminants behavior in marine matrices and support environmental monitoring and preservation strategies.